Preparation of unsaturated ketones



Dec. 23, 1952 w.:G TOLAND PREPARATON OF UNSATURTED KETONES Fld USC. 21, 1946 4 Sheetsfsheet. l

` ATTOPNEKS` Dec. 23,1952 w. G. 'roLAND PREPARATON 0F uNsATURATED KEToNEs 4 sheds-sheet 2 Filedbec, 21, '194e L'HUIO` /234567891011/2/3/4 /1/50 (WT.) Z DUR/NG COMPLEX FORMAT/0N FIG. 2 INFLUENCE oF AMOUNT oF Hso4 PRESENT As BUTENE-'I MERCURIC SULFATE COMPLEX IS FORMED AT 70F ON YIELD OF METHYL VINYL KETONE.

/N VENTOR w/L/A'M 'a ToLA/vo A 7' TURA/EVS Dec. 23, 1952-` w. G. 'roLAND PREPARATON OF UNSATURATED KETONES 4 Sheets-Sheet 3 Filed Dec. 21, 1946 FIG. 3 INFLUENCE oF YARYING AMouNTs 0E L- BIACETYL BuTENE-l |N A MERcuRlc suLEATE soLuTloN coNTATNlNG 5 To 7% H2504 AT eso-65F oN THE YIELos 0E METHYL v|NYL HEToNE. METHYL ETHYL HEToNE AND B|AcETYL.(T|ME 2-3 HRS.)

LL L 20 60 BUTENE-I IN ACID SOLUTION- 96 MERCURIC SALT AS COMPLEX IOO vBV

W. G. TOLAND PREPARATON OF' UNSATURA'VIED KETONES Dec'. 23, 1952 Fred Dec. A21, 1946 uowm wa642 2 zomo ...tmtou @om .w .nii

TEMPERA TURE "F FIGA INFLUENCE 0F sULFURIc ACID CONCENTRATION AND TEMPERATURE oN THE. TIME REQUIRED To oxIoIzE MERCUROUS SULFTE TO MERUCURIC .SULFATE WITH NITROGEN DIOXIDE.

/NVENTOR WILL/AM G. TOLAND A T TORNE K9 Patented Dec. 23, 1952 PREPARATION OF UNSATURATED KETONES William G. Toland, Richmond, Calif., assignor to California Research Corporation, San Francisco, Calif., a corporation of Delaware Application December 21, 1946, SerialNo. 717,654

The present invention relates to the production of ketones having the carbonyl group alpha to a double bond carbon and having a terminal methylene group by liquid phase oxidation of l-olens.

Methods are available for oxidizing the terminal carbon of propylene to the corresponding aldehyde acrolein, but the problem of liquid phase oxidation of olens and particularly the liquidphase oxidation of the carbon not occurring as terminal or on the double bond has not been satisfactorily solved. Usually7 in such oxidations, reaction either takes piace at the double bond, undesirable quantities of a saturated ketone is produced, or the oxidation proceeds to the formation of too much diketones. It becomes evident, therefore, that a method of directing and controlling the oxidation of l-olens to such unsaturated ketones would'substantially advance the prior art.

It is an object of this invention to prepare ketones having the carbonyl group alpha to a double bond carbon and having a terminal methylene group by liquid phase oxidation of l-olens.

It is an additional object of this invention to oxidize l-olens to such unsaturated monoketones during an induction period, said induction period substantially preventing the formation of saturated ketones.

It is another object of this invention to prepare alpha unsaturated ketones having a terminal methylene group by' liquid-phase oxidaition of l-olens during an induction period and controlling the degree of oxidation of said 1- olei-ln to substantially prevent the formation of diketones.

It is a further object of this invention to prepare such ketones from an economical refinery stream fraction treated to remove oleiins interfering with said ketone productions such as butene-2 and isobutylene.

It is an additional object of this invention to selectively oxidize butene-l in a hydrocarbon stream containing butcne-l and butene-Z.

It is a still further object of this invention to prepare methyl vinyl ketone from an economical four carbon refinery stream traction containing butene-2, whereby said butene-2 is converted to butene-l and thereby available for oxidation to methyl vinyl ketone. l

It is another object of this invention to provide a'method of removing substances from the olefin `gas stream which tie up the oxidizing agent making it unavailable for re-use in the 1 Claim. (Cl. 26o-597) '2 Additionally, it is an object of this invention to provide a method for oxidizing l-oleiins substantially to vinyl ketones and treat said ketones to remove color bodies therein. v

Another object is to provide a method for removing water from said unsaturated ketone formed during oxidation of said olens.

A still further object is to provide a method of reoxidizing the oxidizing agent reduced in the oxidation of the said olens.

Another object is to provide a method of obtaining a l-olen in high purity.

A further object resides in providing a method for separating parains from olens.

Briey stated, the process consists of a method of manufacturing an unsaturated alpha ketone having a terminal methylene group which comprises forming a mercurio complex by contacting a l-olen with an aqueous solution or dispersion of an oxidizing agent in a rst reaction stage, said oxidizing agent being a mercurio cornpound capable of forming a complexv with said olefin, and thermally decomposing saidV complex in a second' reaction stage to form said ketone and inhibiting formation of diketones in said decomposition stage by converting at least 25% of said mercuric salt to said olen complex prior to initiating decomposition of the complex, and reducing contamination of said unsaturated ketone with saturated monoketone by effecting both formation and decomposition or said complex within the' inhibition periodI vfor saturated 'mon'- oketone formation'. Y

The" general reactions occurring, for example, in the case of l-butene may be Villustrated as follows:

Reaction A is carried out iirst in the low temperature complex-formation zone of the process and vreaction B is carried out in the high temperature complex-decomposition zone oi the process steps.

It is seen that one molecule of olefin can combine vvith one molecule of mercurio salt. In such a case, all (100 per cent) of the mercurio salt exists as olefin complex. However, since under such conditions per cent of the olen complexed is reliberated in reaction B, it follows that if sufficient olefin is added to form complex with only 25 per cent of the mercurio salt in reaction A, the same reaction could occur in B, since four molecules of mercurio salt are needed to oxidize the olefin to unsaturated ketone occurring on 25 per cent of the mercury salt. Obviously, under such conditions no olefin would be reliberated from the complex. We prefer to operate with at least enough olefin complexed in reaction A to reduce all the mercuric salt present in the reaction chambers to mercurous salts in reaction B. For example, we prefer at least 25 per cent of the theoretical amount of olefin added that can form complex. However, for reasons that will become evident, it is more satisfactory to add sufficient olefin to complex With 50-70 per cent of the mercurio sulfate present.

The foregoing reactions are finite in rate and require an appreciable time interval for completion. This time interval is hereinafter termed induction period for unsaturated ketone formation and designates that period of time required for formation of l-olefin complex plus the time for decomposition of said comp-lex to an alpha ketone having a terminal methylene group.

In making unsaturated ketones by reactions A and B, it has been found that formation of saturated ketones is a competing reaction. The exact mechanism of this competing reaction has not been established, but it is thought that the olefins first are hydrated to saturated alcohols which in turn are oxidized to saturated ketones with resultant contamination of the desired unsaturated ketone product. It has been discovered that the reactions by which saturated ketones are formed have an inhibition period. This term inhibition period is herein used to designate that interval of time Within which the amount of saturated ketone formed is less than about 5% of theoretical.

An important feature of this invention involves the discovery that by proper control of process conditions, principally temperature, the induction period for unsaturated ketone formation can be maintained below the inhibition period for saturated ketone formation to yield an unsaturated ketone of desired purity.

In accordance with the invention, certain operatine factors have definite limits in the induction period. For example, suflicient olefin is add1 ed to the mercurio sulfate acid medium to convert at least 40 to 95 per cent of the mercurio salt to olen complex in reaction A, thereby leaving no mercurio sulfate available after reaction B to oxi dize the ketone to the dketone. Additionally, in accordance with the invention, the conditions under which the complex is formed and held must be correlated within certain temperature and time limits. Furthermore, according to my invention, the conditions under which the complex is decomposed is also preferably correlated within certain prescribed limits of temperature and time.

The procedure is preferably and conveniently carried out in a two-step cold complex formation and hot decomposition process having two reac tion chambers. In the rst chamber the oxidizing agent medium is preferably adjusted to certain degrees of saturation with l-olefin within said inhibition period to form an olefin oxidation agent complex. In the second reaction chamber said complex medium is instantaneously brought to the boiling point still within said inhibition period, to prevent undesirable side reactions such as the formation of saturated ketones, and to decompose said complex and form the desired un,-

'4 saturated ketone and a corresponding reduction product of the oxidation agent.

These two chambers may be referred to as the olefin-complex forming chamber and the olefincomplex decomposing chamber, respectively. A preferred method of operation comprises adding the olefin-containing gas at such a rate and temperature that the oxidizing agent becomes about 40 to 95 per cent complexed within the inhibition period.

Operating with at least 25 per cent of the mercurio salt in the form of olen complex leaves little available to carry the oxidation reaction too far, such as the oxidation of ketone to diketone, and saturating below 60 F. and preferably be tween 40 F. and the freezing point prevents undesirable reactions such as the formation of saturated ketones.

The addition of sufficient olefin to unite with 40 to per cent of the oxidizing agent results in the formation of the complex illustrated in reaction A. In the low temperature chamber during formation of said olefin complex, the unreactive liquid or gaseous paraffin hydrocarbons separate from the reaction mixture by suitable methods such as decantation or vaporization, thereby providing a means of separating parafns from olefins. The olen fraction now bound to the mercury salt during the induction period is conducted to the complex decomposing chamber maintained in the temperature range of 180 F. to 240 F. where the complex is instantly broken to form the ketone, as illustrated in reaction B.

Since four equivalents of mercurio sulfate are required to oxidize one equivalent of olefin, it follows that at per cent reaction of the mercury (complexed as in reaction A) only 25 per cent of the olefin bound in said complex is oxidized to ketone. The remaining 75 per cent of olefin in the complex reverts to free purified l-olefln and may be either recycled back to the first reaction chamber to unite with more oxidizing agent, or may become a source of puried olefin for other purposes such as the preparation of olefin oxides such a-s butylene oxide.

Said portion of induction period dealing with olefin-mercurio sulfate-complex formation and methyl ethyl ketone formation varies with temperature and time as shown in Table I.

TABLE I Methyl Ethyl Ketone in Total Kctonc, Wt. Percent Time (Hrs.)

The data show that subjecting butene-l-Inercurio sulfate complex to a temperature of 18 to 22 F. for 1 hour gives no ne of the saturated compound methyl ethyl ketone, whereas subjecting said complex to this temperature for 1.5 hours results in 2.7 per cent of methyl ethyl ketone in the final reaction products. Likewise, the data show that if said complex is held at 70 F. for 1 action (Distribution fof methyloinyl ketone) .ffhcurs astmuchms-;8; perf.cent.ohtheiisaturated .ketone-appears ,in fthe `desiredYunsaturatedketone zllroduct Additionally, ..the fi table #shows Athat longer periods :aridvhigher.l vtemperatures produce :stillgreater "amounts oi-the lundesired. methyl l.;

``ethyl ketone.

. Additionally, we have discovered that .even after .the complex Yispreferably formedfunder: said conditions .of lowv A,temperature .andbshort v.-time, `additional precautions .must bev exercised-in :the v., decomposition ,of said complex ,to-the unsaturated ketone. For` example, it has been discoveredthat :unless thee-.temperatureof said complex is :almost Ainstantaneously broughtv to 'the v `boilingV` point, substantial amounts vof .saturated ...v -ketone.; may

form; that the. unsaturated` ketoi'nei.mayl vhe idestroyed by the acid, or the oxidation may be-.cav

ried .too,;far. sQperating rconditionsfiable ,ID

.in which v.abutene-1fmercuricsulfate complex is quicklyy .brought V`to yboiling temperature, -held wat.; Such .temperature Afo1'..a lf.evvminutes while .methyl vinyl ketone is lstripped out.. inunediatelyvgchilled to .below Aroom temperature;'filtered,-1Washedand vanalyzed `shows-the .distribution of :methyl vinyl vketone and .indicates the; speed `With which reaction Boccurs.

TABLE II Influence `of reaction.tmeot2124215" ort-rc- A,Reaction Time-min :3A v-.Ei @54j Methyl Vinyl Ketone .stripped during reaction, percent :MethylfVinylKetc-ne:

from Filtrate;percent from HgzSO4 wash water, percent.

rNumber of Washes.

theboiling point by adding the reactiorrprodu'cts lto `1000parts of stirred boiling 10%' `sulfuric.,acid

1through which Asteanris passing. "The "methyl vinyl ketone as 4v'formed isthereby' continuously and.-rapidlyremoved Within the' inhibition period for saturatedketone formation.

EXAMPLE `II Pentene-l lis reacted fzwth va sulfuric-'acid solution of vmercurio sulfate using Lthe lprocedure .in

Example I. The product isethylivinylketone.

EXAMPLE III 'Octene-'l .is reacted `with .a Vsulfuric .acid solution of mercurio acetate using"theprocedure in Example I. 'Theiprojductjis pentylfvnylketone.

Ytonefe per. cent is methyl ethylA ketone fand- 3 nXA-MPLELIV .The oleiin-complex formation chamber 'is charged with 1l00pa`rts of waterand -1-100parts of mercurio:sulfatecontaining?31Weight percent .of` .sulfuricacid Tothis-"mixture *at 260 -is addedfa .gael/comprising.87.1; per cent '.butene-l 1andg4i52gfper cent butene-,2.A Said gas is 4added ...until 60; :formed: thenbutene-l .-mercuric sulfate complex. -Ater :being held A30 minutes the -butene1 mer- 1 curio sulfate reaction mixture nis then l.transferred during v`3D1-additional minutes to ythe olen-com- .Vplex decompositionfchamber containing a soluer @cent :of the mercurio sulfate `has ftionbf'hot 12-per-cent sulfuric acid from the .previous run, While simultaneously stripping with fsteamto -removeketones, at such Va rateas to .decompose `thecornplex asv added, thereby liberat- .ing=loleins,.ketones' and water as vapor. 'Stripping .is continued `one-half hour l after `all slurry fare econdensedein a` Water .condenserland .the

isznadded. y .The methylvinyl ,ketone .and -Water .liberated Ihutene.- 1 is. condensed 1 in a `trap .cooled by-'Dry Ice. --Totalfketone yield based on 1butene and 2-butene in the feed is 97499 per cent of theoryof which 93 percent is methyl vinylke- .per centis biacetyl.

:EXAMPLE v The l'olefin-con-lplex formation chamber *lis =charged`=withf1100 parts o'f water and y1'100"pa'1"ts -olcrnercuricsulfate containing 3 vWeight per cent Iofl free-sulfuric acid. To this mixture at 60 F.

"is :added'a `gas comprising 87.1 per cent butene-l 'fand-14.5'2'fper cent 'butene-2. 'Said gas is vadded "'ur'itil-60-perfY cent lof the mercurio sulfate has -form'edithe butene-'l f" mercurio sulfate complex.

After being held SOminutes the butene-l mercurio sulfate reaction mixture is transferred dur- .35f-ing" 30 additional minutes to the olefin-complex "decomposition-*chamber containing a'solution of vvhot `12 percent sulfuricacid 'from the previous `run,' z`While vsimultaneously stripping with steam lto remove ketones, at such a rate vasto decomv-pose the complex as Yadded thereby liberating olens; ketones,` and water as vapor. 'fis -continuedvone`half heurt-after all slurry is *added The methyl'vinylketone and water are Stripping 'condensed ina water condenser and the' liberated ffbuteneS-lis condensed inar trap cooledby Dry ilse. :Conden-sate "(1170 cc.) containing 5.08 vper cent fo'fmethyl vinyl ketone is obtained. This fisequivalent' to'59.4 grams of 95 mole per cent Abasedfon mercurio sulfate.

preferred method of oxidizing an olen to -alketone byjthe'cold'absorption process may be 4carried out" bythe-details shown in 'Figure",1.

In .this flow process a l-olen such as butene-l.

"which Vmayl contain paraflinsisconveyed by line l' to saturator l2. Similarly, theoxidizing-'me- `'dium'- which may consist'of mercurio, sulfate, A"sulfuricacid and water is conveyed by line Il to vsaturator I2. The alosorptionofbutene-l in rthe -mercuric sulfatev acid mixture is` carried out at a temperature below V68" 'E'. and preferably below140 `F.""to prevent hydration ofthe ol'en vr'such"as'butene-l which would lead'to methyl ethyl ketonelcontamination of .methyl V.vinyl lketone. Para'ins, such as butane, leave the sysitem byline '13. The solution of mercurio sulfate- .buten'e-l-comp'lex Vleaves the saturator via line fhl` and is transferred to vreactor and stripper I6,

heldat'a-temperature of about 180 F. to about A124:0 F. wherein said `addition product is decomipose'd 'to form the rdesired methyl vinyl ketone. Said ketone, water and liberated olefin by line 'Il -is -conveyed 1z0-"stripper I8 vvhere the ketone fand Wat'erfa're separated from the liberated olen vrtv'hichreturnsby lines 19 and I0 'to thesaturator to Iiorml more mercurio sulfate-olen-complex Line 2I carries the reaction products comprising 5 to 20% of ketone such as methyl vinyl ketone and water to the distillation unit 22 where part of the water is removed at line 23. The ketone rich azeotrope is conveyed by line 24 to dehydrator 26. Lime (CaO) in the amount of 0.1 per cent by weight, serves to throw color bodies into the water layer and enters the dehydrator by line 2l. A hydrocarbon boiling in a suitable range, such as isopentane, enters by line 28 and serves to extract the ketone from the water. The lime, water, and color bodies leave the dehydrator by line 29 and the hydrocarbonketone liquid such as isopentane and methyl vinyl ketone are conveyed from the dehydrator to distillation unit 32 by line 3l. The hydrocarbon is recycled to the dehydrator by line 28 while the dry ketone is conveyed by line 33 to storage 34.

The spent oxidation mass consisting of the reduced salt such as mercurous sulfate, an oxygencontaining acid such as sulfuric acid and water, leaves the reactor I6 and is conveyed by line 36 to filtration unit 31. Part of the filtrate consisting of the acid and water are conveyed by lines 54 and 56 to dissolver 53 where they contact mercuric sulfate and are recycled to the saturator I2 by line I I. The separated mercurous sulfate from ltration unit 3l is conveyed by line 38 to the oxidizer 4I where it is oxidized to mercuric sulfate and conveyed by line 49 to filtration unit 5I and then recycled to the saturator as already described.

'I'he reduced form of the oxidizing agent such as mercuric sulfate may be re-oxidized by any suitable procedure. A preferred method consists of a solution containing nitric acid, nitrosyl sulfuric acid, sulfuric acid and water at 200-275 F. fed to oxidizer 4I by line 39. The nitrogen oxides oxidize the mercurous sulfate and said nitrogen oxides in a reduced state are conveyed by line 42 to oxidizer 44 and re-oxidized by air at a temperature of about '70 F. Air enters oxidizer 44 by line 43 and line 46 conveys the oxidized nitrogen oxide to absorber 41 which separates said oxidized nitrogen oxide from the spent air. The spent air leaves absorber 41 by line 4S. The oxides are adsorbed in concentrated sulfuric acid in absorber 4l to yield the original oxidizing mixture of nitric acid, nitrosyl sulfuric acid and sulfuric acid. They are then recycled through line 39 to oxidizer 4I.

The re-oxidized HgSO4 and oxidizing-mixture from oxidizer 4I is sent to a filter unit 5I by line 49, and the I-IgSO4 removed and sent to dissolver 53 through line 52. The spent sulfuric acid mixture is conveyed by line 58 and reconcentrated in unit 59 before recycling to the nitrogen dioxide absorber by line 62.

The data in Figure 2 show the influence of the amount of sulfuric acid present as the butene- 1-mercuric sulfate-complex is formed at 70 F. and broken at 215 F. on the yield of methyl vinyl ketone. The data disclose the yield of methyl vinyl ketone to be as high as 85 per cent and critical in the range of 0.25 to 3.0 weight per cent of acid. Lower complex formation temperatures displace the curve upwards so it approaches yields of 100 per cent of theory at 40 F. and 1 per cent sulfuric acid.

The data in Figure 3 show the influence of the degree the mercuric salt is complexed at 5 to '7 per cent sulfuric acid at 60 to 65 F. on the yields of methyl vinyl ketone and biacetyl. The data show that adding butene-l to the medium to the level of 40 per cent of the mercuric salt as complex gives yields of 56 and 5.5 per cent of theory of methyl vinyl ketone and biacetyl, respectively, based on butene-l. However, by adding butene-l to the medium to the level of per cent of mercuric salt complexed yields of 76 and 2 per cent of theory of methyl vinyl ketone and biacetyl, respectively, based on butene-l are obtained, Lowering the temperature below 65 F. during complex formation and reducing time for complex formation and decomposition to less than 1.5 hours, lowers the curve for methyl ethyl ketone formation and raises that for methyl vinyl ketone formation so that below 40 F. conversions to methyl vinyl ketone approach 98% of theory.

A preferred method of re-oxidizing the oxidizing agent is disclosed in Figure 4 wherein the influence of sulfuric acid concentration and temperature on the time necessary to oxidize mercurous sulfate to mercuric sulfate with nitrogen dioxide is shown. In the temperature range of 200 to 275 F. a period varying only a few seconds to 20 minutes, respectively, are necessary to completely oxidize the mercurous sulfate to mercuric sulfate. While this is a preferred method, the process is not limited to this procedure.

Products emerging from the low temperature complex-forming chamber may consist of the olen-oxidizing-agent-complex, water, acid, unreacted oxidizing agent and inert gases present in the olen source, such as paraiiins.

Products emerging from the high temperature complex decomposition chamber may consist of the ketone formed, acid, a reduced form of the oxidizing agent, a small amount of unreduced oxidizing agent, small and varying quantities of diketone, the liberated purified olen, varying quantities of 2oleiin depending on Whether the isomerization step is practiced, and small varying quantities of the diinculty decomposable iso-olen complex such as isobutylene mercuric sulfate complex.

A typical renery stream containing olefins suitable for oxidation to methyl vinyl ketone usually contains varying amounts of butane, isobutane, butene-l, butene-2 and isobutylene. It has been discovered that the oxidation of butenel in such a feed stock with mercuric sulfate shows no oxidation of the butene-2 fraction under proper induction period conditions. In fact, it has been discovered that by suitable control the butene-,2 may be retained unchanged in this selective'oxidation reaction step and separated as such. Recycle of butene-2 with the butene-l stemming from the decomposing mercuric sulfate olerln complex is possible but such butene-Z, if present in appreciable quantities in refinery streams, accumulates and dilutes the recycle butene-l stream and ultimately seriously interferes with the oxidation of butene-l to methyl vinyl ketone. Additionally, butene-2 tends to form methyl ethyl ketone which complicates purification and recovery.

Another problem is presented by isobutylene present in the now stream during the oxidation of butene-l in an induction period. Said isobutylene forms a mercuric-sulfate-butylene-complex so stable it is not decomposed during said unsaturated mono-ketone formation from butene-1l complex. Since this complex is not decomposed, part of the oxidizing agent is removed from participation by being tied to a stable complex. As such the stable complex circulates with asesora the reduced; portion of the: oxidizing" agent and must be burned out duringreoxidation of the oxidizing. vagent at. additional. expense'.v` Such treatment `is f costly` and disturbs the timirl'gvv andi economy ofY the-process. Thisy posesthe.: problem of either `removingsaid isobutylenei'from'theifeedi ortreating said stable complexby some1 pro;- cedure" sufficiently drastic to.- liberate:` the4 oxidizi-V ing-.agent thereby'makingitavailable for-'.reuse.V

It is, therefore, an additionalpart of-.thisf-.inx-4v vention to solve the butene-2 and isobutyleneproblems by conditioning a suitable refinery stream-such as one containing substantially three andlfour carbon compounds such-Las propyl'ene, butane, isobutane, butenel,Y butene-Z and'- iso-f` butene-2 as bottoms; beA isomerized.- to butene-l by va convenient catalystfsuch as-copper oxide or nickel on 1=c` rocella`tI` a temperatureof 600lto11,000 The'productsi of said somerization step may-be passed through the later described-sulfuric acidadsorptionchamberto lseparate any isobutane for-med during iso merization of`r butene-2 to butene-l The overheadfrom-said super-fractionatorcontaining paraffms, butene-l andisobutylene is passed through 60%- sulfuric` acid` preferably maintainedu below-` 100" Fito selectively absorb isobutylene, thereby purifying said hydrocarbon stream. now containing substantially butene-l;

capable of being oxidized tofmethyl vinyl ketone bymercurio sulfateand -varying amounts 'of come pounds Vunreactiveunder said preferredsoondition to mercurio sulfate, such asbutane, *isobutanef and any small amount of butene-Z/-notremoved` by the super-fractionating column or not isomerized.

However,` ifA butene`-2 iswantcd' involurnein a puried form,` the" isomerization` step maybe' omitted for it has been discovered that butene1-1 and butene-Z are absorbed'in an aqueous dispersion containing a mercurio compound which forms a complexAk with'V buteneel; saidw complexn thermallyl decomposing in a' second" reaction" stage to selectively oxidize lbuten'ed to'an une' saturated ketone while separating. butene-2 with'- out" substantial oxidation by" decomposing said. complex and vaporizing, said absorbed buteneiZ;

the-'oxidation of "butene-Zibeing prevented during' butenef-'l oxidationwithin the' induction period for 'unsaturated ketone formation and'within' the" inhibitionperiod for saturated'ketone formation; The concentrated butene-2 may be removedfrom the recycle'flow stream'by'c'onventi'onal methods.

Many` additional operating steps the flowV sheet either `are 'quite critical 'ormay be "operated" under`- certain specified 'conditions asfollows' Omidzngagentsf @ther mercury saltsthan mercuricsulfate such asv mercurio phosphatelv and mercurio' acetate; have been found to give results. However', the

sulfate is preferred, since it presents fewer'problems andgives-go'od results.- Itisto belunderstoodf that the physical characteristicsof the` various-oxidizing agents contemplatedby the in' ventionl. will depend upon' theirconcentration the.; aqueous medium andmay appear as' an los aqueous dispersion or asi a solution;` For the sake of clarity in the" description' of"l the* inver1`= tion inl the' specification and claims; reference Will ybernade'to the term dispersion which-isi to'be interpreted inl agenericsense embracing molecular aswell as colloidalv dispersions:

Ratio oisulfuric acierto mercurio-sulfate.;

The reduction of" mercurio ysulfate is.l attendant-4 HgS O4 in .Slurry in eSaturatorg' Percent Reactor,

Percent the resulting acid solution as the complex decomposes. Additionally, the strongerthe resulting acid' solution, the more easily said acid solution is concentratedl inY thecatalyst regeneration unit. However, strong sulfuric acid solutionsdestroy the ketone and lowyieldsv4 result, whereas with little or no acid pri-:sentl inlthe slurry, the rate of Vdecomposition of'thea'complexl on heating is to'o low `for desired results: The'V balancing of 'these' factors dictate a slurry in an operative rangev containing"'aboutl 3-#70l weightI percentof'mercuric sulfate; Apr'eferre'd range comprises about 20 to 60weight per cent" of mercurio sulfate While the optimum rangecorn' prises 45 to 55 weight per cent-of mercurio sulfate. The latter introduces' about"12 to 17 per cent sulfuric acid inv thefolefin-oomplex` decompositionchamber.

The temperature offthel mercury-olefin come* tion, namely the hydrationk ofthe: olefin to the* alcohol. This competing reactionbecomes lquite marked' in the presenceof sulfuric acid atrele` vated temperatures; If this reaction is'allowed to occur thealcohol so formed is oxidizedto 'the' saturated'ketone during thefhigh temperature complex-decomposition period; Inorderto 'avoidicontamination of theunsaturated"ketone with" such undesirable products, conditions'of time; temperature and concentration are so control-led asherein already referred' to by carr'ying out said reaction in the induction'p'eriodforunsat- .Formedin urated ketone formation within the inhibition period for saturated ketone formation to decrease or prevent the formation of said competl ing reaction and simultaneously permit the desired oxidation reaction to proceed at maximum rate. However, in the case of a pure olefin feed, both complex forming and complex decomposing reactions may be simultaneously carried out in one chamber in an induction period for unsaturated ketone formation Within an inhibition period for saturated ketone formation.

Degree of saturation of olefin in the dilute acid mercurio salt solution The olefin unites with the oxidizing agent to form a complex in a 1:1 molar ratio of olefin to mercuric sulfate. However, only 25% of said olefin on the complex is oxidized to ketone, the rest being reliberated as olefin.

Inorder to direct and control said oxidation of olefin to said unsaturated mono-ketone, it becomes desirable to add more olefin than can react with the available mercurio sulfate to insure removal of substantially all of the mercurio sulfate and thereby keep diketone formation at a minimum. At the same time it is desirable to refrain from adding considerably more olefin than will theoretically react, to keep adsorption time at a short practical period. In the solution of these problems it has been discovered that olefin to the extent of 40 to 95 per cent of that capable of coinplexing with the oxidizing agent comprises an operative range, whereas 50 to 85 per cent comprises a preferred range and 60 to 80 per cent comprises an optimum range for keeping the yield of diketone low without adversely affecting unsaturated mono-ketone yield.

An additional advantage derived from complexing more than 25 per cent of the mercurio sulfate with olefin is the discovery that the induction period is decreased as more of the mercury salt is complexed. However, the higher the concentration of complex the greater the tendency'for the hydration reaction to proceed. Balancing of these factors gives an optimum range of 60 to 80 per cent of the mercuric salt complexed.

Flow rates to the olefin complex forming chamber "The rate at which the olefin is fed to the olefinmercurio sulfate-complex forming chamber depends on the concentration of olefin in the gas feed. A gas containing about 25 per cent olefin at a temperature of about 60 F. has shown that one thousand grams of oxidizing medium containing 22.2 per cent mercuric sulfate will absorb 95 per cent of 2 moles of l-butene per hour. The reaction is very rapid, the contact time being about four seconds. Since the absorption process is exothermic, the chamber preferably should be cooled during absorption of the olefin to keep the temperature down. This may be accomplished by means of Acooling coils, a cooling jacket, flowing the olefin from a high pressure line to a low pressure absorption chamber, thereby utilizing the cooling attendant with vaporization, or any other suitable cooling process or device.

y With a relatively pure olefin feed, butene rates have been used, at room temperature, with good absorption results in the range of 0.5 to 4.5 moles per hour which corresponds to a range of from 49 to 437 volumes of gas per volume of complexforming chamber per hour. The maximum rate of absorption was not reached.

12 Flow rates to the olefin complex decomposition chamber Solutions of the complex have been passed up to 8600 grams per hour or about 30 volumes of liquid containing the complex per volume of reaction chamber. Ihe maximum rate was not reached. A preferred procedure is to add the olefin complex at such a rate and under such conditions that it rapidly and preferably instantly reaches the boiling point.

Decomposz'ng the olefin-mercurio sulfate complex The most critical factor relating to the decomposition of the olefin-mercurio sulfate complex to form unsaturated ketone and liberated olefin is the speed with which said complex is heated to the reaction temperature of about 180-240" F., and the speed with which the unsaturated ketone is removed from the reaction zone.

Very good results have been obtained by heating the reaction chamber by a steam jacket and adding new complex to the boiling slurry from which the complex is decomposed While simultaneously stripping with steam. The stripping steam removes the unsaturated ketone and excess olefin from the acid mass, as formed, thereby diminishing further undesirable reactions.

The evolution rate of the pure unoxidized olefin is very rapid and is completed in a few seconds after the complex reaches a temperature of about 215 F. Evolution of the unsaturated ketone is slower, being stripped out in 6 minutes at boiling temperature. (Table II.) The remainder is largely removed after 1 hour of stripping. The use of higher temperatures and pressure may be used to cut down stripping time. An alternative to the final stripping in a separate unit consists of retaining the last 20% of unsaturated ketone in solution until the mercurous sulfate is filtered off, then flashing it off in a film vacuum concentrator while concentrating the sulfuric acid.

Yields Yields of -98 per cent of theory of unsaturated ketones based on 1olen have been obtained.

While the process has been illustrated by numerous examples, it will be apparent to those skilled in the art that various modifications may be made in carrying out the process while retaining the benefits of the discoveries herein disclosed.

Additionally, the method is applicable to other olefins than butene-l, for example, 2-methyl pentene-l yields methyl isopropenyl ketone. Furthermore, normal pentene-l, isopentene-1, alpha hexenes, alpha heptenes and alpha octenes, dienes, butadienes, isoprene and pentadiene, may be used.

However, with ethylene there is no allyl carbon to be oxidized and hence, the olefin is reliberated as ethylene. In this instance, the method acquires an additional value, thereby providing a means of separating and purifying ethylene from a feed containing ethylene, saturated hydrocarbons, or other gases such as oxygen, nitrogen, hydrogen or mixtures of two carbon and lighter hydrocarbons.

I claim:

A process of manufacturing methyl vinyl ketone which comprises absorbing a mixture of butene-l and butene-2 in an aqueous sulfuric acid dispersion of mercurio sulfate to form a butene-l complex, and selectively oxidizing Abutene--l to methyl 13 vinyl ketone Without corresponding oxidation o1' hydration of butene-2 by effecting said absorption at a temperature below about 60 F.; selectively releasing butene-Z from its absorbent by raising the temperature of said aqueous dispersion to- 5 gether with its absorbed olens to the boiling point through the range above about 60 F. substantially instantaneously to limit butene-Z residence time at temperatures above 60 F. and inhibit oxidation of said butene-2; and decomposing 10 said complex to form methyl vinyl ketone.

WILLIAM G. TOLAND.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,315,541 Curme Sept. 9, 1919 2,348,931 Schulze May 16, 1944 2,388,510 Voge Nov. 6, 1945 2,398,685 Yale et al Apr. 16, 1946 2,403,671 Matuszak July 9, 1946 2,424,186 Packie July 15, 1947 

